EP0067308A1

EP0067308A1 - Neutralizing layer for color transfer assemblages

Info

Publication number: EP0067308A1
Application number: EP82104056A
Authority: EP
Inventors: John Francis Bishop; Wayne Arthur Bowman
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 1981-05-14
Filing date: 1982-05-11
Publication date: 1982-12-22
Also published as: CA1162093A; JPS6245544B2; DE3262760D1; EP0067308B1; JPS57195243A; US4389479A

Abstract

Photographic color transfer assemblages are described employing a novel neutralizing layer comprising a cross-linked polymer having recurring units of an N-(alkoxymethyl) acrylamide, an acrylic acid and an alkyl acrylic ester.

Description

This invention relates to photographic assemblages for color diffusion transfer photography wherein a novel neutralizing layer is employed. This neutralizing layer comprises a cross-linked polymer having recurring units of an N-(alkoxymethyl)-acrylamide, an acrylic acid and an alkyl acrylic ester.
Various formats for color, integral transfer assemblages and for so-called "peel-apart" assemblages are described in the prior art. In such assemblages a "shut-down" mechanism is needed to stop development after a predetermined time, such as 20 to 60 seconds in some formats, or up to 3 minutes, or more, in other formats. Since development occurs at a high pH, it is stopped by merely lowering the pH. The use of a neutralizing layer, such as a polymeric acid, can be employed for this purpose. Such layer also serves to stabilize the element after the required diffusion of dyes has taken place. As the system starts to become stabilized, alkali is depleted throughout the structure, causing silver halide development to cease or to slow down in response to this drop in pH. For each image generating unit, the shutoff mechanism establishes the amount of silver halide development and the related amount of dye formed according to the respective exposure values.
Experiences with neutralizing layers has shown that they should be hardened, i.e., cross-linked, in order to avoid problems associated with loss of adhesion. The latter occurs after neutralization and is believed to be caused by formation in the neutralizing layer, of water soluble alkali metal (e.g. potassium) salts.
A common cross-linking agent for neutralizing layers comprising acrylic acid polymers and copolymers is a bis-epoxide hardener such as Araldite RD-2_. (Ciba-Geigy) which is believed to be 1,4-butanediol diglycidyl ether. However, when such a hardener is employed, unreactive epoxide, or other fragments of the hardener, migrate out of the neutralizing layer and change the properties of the adjacent timing layer thereby causing loss of physical integrity of the timing layer.
Accordingly, a need exists for a neutralizing layer which has good swell characteristics, adhesive properties, physical integrity and stability, which does not require a separate cross-linking agent and yet can be internally cross-linked or hardened.
The present invention provides a photographic assemblage comprising:

(a) a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material;
(b) a dye image-receiving layer;
(c) a neutralizing layer; and
(d) a timing layer located between the neutralizing layer and the dye image-receiving layer so that processing composition must first permeate the timing layer before contacting the neutralizing layer;
characterized in that said neutralizing layer comprises a cross-linked polymer derived from:
- i) 5 to 30 weight percent of recurring units having the structure:
  wherein
  - R¹ is hydrogen or methyl;
  - _R ² is alkylene (straight or branched) having from 1 to 10 carbon atoms such as methylene, ethylene, propylene, trimethylene or tetramethylene; arylenealkylene having from 7 to 15 carbon atoms such as phenylenemethylene, phenyleneethylene, or phenylenetrimethylene; alkylenebisarylene having from 13 to 20 carbon atoms such as methylenediphenylene or isopropylidenediphenylene; arylenebisalkylene having from 8 to 15 carbon atoms such as phenylenedimethylene or phenylenediethylene; or arylene (substituted or unsubstituted) having from 6 to 16 carbon atoms such as phenylene, naphthylene, or biphenylyl- ene;
  - _R ³ is an alkyl (including substituted alkyl) group of 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, isobutyl, octyl, 2-ethylhexyl, isononyl, or decyl; and
  - n and m are 0 or 1 with the proviso that when m is 0, n is 0, and when m is 1, n is 0 or 1;
- ii) at least 30 and up to 90 weight percent of recurring units derived from a substituted or unsubstituted acrylic acid; and
- iii) 5 to 30 weight percent of recurring units derived from an alkyl acrylic ester wherein the alkyl group has from 1 to 16 carbon atoms.

Preferred cross-linked polymers are those wherein n and m are each 0 and where R¹ is hydrogen and R³is an isobutyl group. Examples of N-(alkoxymethyl)acrylamide monomers useful in this invention include the following:

N-(isobutoxymethyl)acrylamide
N-(methoxymethyl)acrylamide
N-(methoxymethyl)methacrylamide
N-(ethoxymethyl)acrylamide
N-(isopropoxymethyl)acrylamide
N-(s-butoxymethyl)methacrylamide
N-(isohexoxymethyl)acrylamide
E-[N-(t-butoxymethyl)carbamoyl]styrene
N-[2-(N-isobutoxymethylcarbamoyl)ethyl]-acrylamide
N-[3-(N-isobutoxymethylcarbamoyl)-propyl]acrylamide
N-[4-(N-isobutoxymethylcarbamoyl)-butyl]methacrylamide
N-[2-(N-isopropoxymethylcarbamoyl)-ethyl]acrylamide
N-[3-(N-isopropoxymethylcarbamoyl)-propyl]acrylamide
N-[4-(N-isopropoxymethylcarbamoyl)-butyl]methacrylamide
N-[4-(N-isobutoxymethylcarbamoyl)-phenyl]acrylamide
N-[4-(N-isobutoxymethylcarbamoyl)-phenyl]methacrylamide

Substituted acrylic acid monomers which can be employed in the neutralizing layers include the following:

acrylic acid
citraconic acid
a-chloroacrylic acid
methacrylic acid
fumaric acid
monoethyl fumarate
monomethyl fumarate
monomethyl itaconate
itaconic acid
maleic acid
mesaconic acid
a-methyleneglutaric acid
crotonic acid
monodecyl itaconate
manododecyl itaconate

It is preferred that the acid moiety of the polymer is either acrylic acid or methacrylic acid.
Suitable alkyl acrylate esters having from 1 to 16 carbon atoms which may be employed in the polymer described above include the following:

t-pentyl acrylate
n-pentyl acrylate
1-ethylpropyl acrylate
n-butyl acrylate
benzyl acrylate
t-butyl methacrylate
t-butyl acrylate
4-chlorobutyl acrylate
cyclohexyl acrylate
cyclopentyl acrylate
cetyl acrylate
cyclohexyl methacrylate
2-chloroethyl methacrylate
2-chloroethyl acrylate
ethyl methacrylate
isobutyl acrylate
2-ethylhexyl acrylate
n-hexyl methacrylate
2-ethyl-l-methylbutyl acrylate
2-ethylhexyl methacrylate
n-butyl methacrylate
isobutyl methacrylate
isopropyl methacarylate
lauryl acrylate
lauryl methacrylate
methyl acrylate
methyl a-chloroacrylate
methyl methacrylate
n-octyl acrylate
n-octyl methacrylate
ethyl acrylate
propyl acrylate
3-chloropropyl acrylate
n-hexyl acrylate
2,2-dimethylbutyl acrylate
neohexyl acrylate

The alkyl acrylate ester moiety of the above polymer preferably comprises an alkyl acrylate or methacrylate wherein the alkyl group has from 1 to 6 carbon atoms. Butyl acrylate is especially preferred.
As described above, the neutalizing layer is a cross-linked polymer. Cross-linking can occur by either an acid-catalyzed mechanism or a thermal mechanism. According to American Cyanimid Company Process Chem. Dept. Bulletin PRC 126, dated February 1976, entitled "IBMA Monomer N-(iso-butoxymethyl)-acrylamide," these cross-linking mechanisms for the N-alkoxymethyl acrylamide monomer are believed to occur in the following manner:

Acid-Catalyzed Cross-Linking Mechanism

In the acid-catalyzed mechanism there can be employed, for example, p-toluenesulfonic acid, phosphoric acid, sulfuric acid, or virtually any alkyl or aromatic acid such as poly(vinylsulfonic acid) or poly-(2-acrylamido-2-methylpropanesulfonic acid). Good results are obtained when the acid catalyst is used at 1.5 percent of the weight of the polymer.

Thermal Cross-Linking Mechanism

In the first step, thermal condensation yields intermediate structure I and an alcohol as the only cleavage product. This intermediate can be then hydrolyzed to give the cross-linked structure shown.
Thus, it is seen that the N-(alkoxymethyl) acrylamide monomer internally cross-links or self- hardens in the presence of heat or an acid as a catalyst. This eliminates the need for a separate cross-linking agent.
The polymeric neutralizing layer can be coated at any amount which is effective for the intended purpose. Preferably, it is coated at a coverage in the range of 40 to 100 milliequivalents acid/m², depending upon the alkali content of the activator which is to be neutralized.
In a preferred embodiment of the invention, the assemblage contains an alkaline processing composition and means containing same for discharge within the film unit. There can be employed, for example, a rupturable container which is adapted to be positioned during processing of the film unit so that a compressive force applied to the container by pressure-applying members, such as would be found in a camera designed for in-camera processing, will effect a discharge of the container's contents within the film unit.
The term "nondiffusing" used herein has the meaning commonly applied to the term in photography and denotes materials that for all practical purposes do not migrate or wander through organic colloid layers, such as gelatin, in the photographic elements of the invention in an alkaline medium and preferably when processed in a medium having a pH of 11 or greater. The same meaning is to be attached to the term "immobile". The term "diffusible" as applied to the materials of this invention has the converse meaning and denotes materials having the property of diffusing effectively through the colloid layers of the photographic elements in an alkaline medium. "Mobile" has the same meaning as "diffusible".
The term "associated therewith" as used herein is intended to mean that the materials can be in either the same or different layers, so long as the materials are accessible to one another.
The following examples are provided to further illustrate the invention.

Example 1 Synthesis of Poly[n-butyl acrylate-co-acrylic acid-co-N-(isobutoxymethyl)-acrylamide], 20:70:10 weight ratio

A mixture of 3800 g acetone and 1900 g distilled water were added to a 12 1 flask equipped with a stirrer and condenser. The mixture was degassed with nitrogen for 15 minutes and placed in a 60°C bath. Next 13.0 g 2,2'-azobis(2-methylpropionitrile) were added. Immediately afterwards a mixture of 200 g n-butyl acrylate, 700 g acrylic acid, and 118 g of an 85 percent solution of N-(isobutoxymethyl)acrylamide were added from a 2 1 header flask over a period of 40 minutes. The resulting polymer solution was then stirred at 60°C for 16 hours. The clear viscous polymer solution was then cooled and the polymer was precipitated in 56 ℓ of distilled water. The "soft-taffy" product was washed twice with distilled water and redissolved in 4.8 ℓ of acetone to give a clear viscous solution contaning 10.9 percent solids.

Example 2 Swell Characteristics -- Physical Integrity

(A) A control element was prepared by coating on a poly(ethylene terephthalate) film support a neutralizing layer of poly(n-butyl acrylate-co-acrylic acid) (30:70 weight ratio) equivalent to 81 meq. acid/m², hardened with 1,4-butanediol diglycidyl ether.
(B) Another control element was prepared by coating on a poly(ethylene terephthalate) film support a neutralizing layer of poly[n-butyl acrylate-co-acrylic acid-co-N-(isobutoxymethyl)acrylamide] (20:70:10 weight ratio) equivalent to 48 meq. acid/m² (unhardened).
(C) An element employing the neutralizing layer of the invention was prepared similar to (B) except that it was hardened with 1.5 percent p-toluenesulfonic acid.

The above coatings were prepared from 80/20 acetone/water solutions of the indicated polymer using conventional coating techniques. Drying was for a total of 5.5 minutes, stepped from 77°C to 21°C (dry bulb).
The swell of each coating in µm was measured using standard techniques with a probe-type hydraulic swellometer by immersing in an activator of the following composition:
The swellometer was similar to the one described by F. M. Flynn and H. A. Levine in Photogr. Sci. and Engr., 8, 275 (1964). The following results were obtained:
The above data indicates that Element C employing the neutralizing layer according to the invention has superior swell characteristics (smaller amount of swell) compared to the Control Element A, which also lost physical integrity after 30 sec. The data also indicates that the neutralizing layer according to the invention must be hardened in order to maintain physical integrity (Element C compared to Element B, which lost physical integrity after 5 sec). Good physical integrity is necessary for adhering other layers on top of a neutralizing layer.

Example 3 Photosensitive Element Test

Photosensitive (donor) elements were prepared by coating the following layers in the order recited on an opaque poly(ethylene terephthalate) film support:

(1) Neutralizing layer of Example 2, Elements A and C
(2) Interlayer -- See Table II
(3) Timing layer
(4) Interlayer of "gel nitrate"
(5) Cyan redox dye-releaser layer
(6) Red-sensitive, negative-working, silver halide emulsion layer
(7) Interlayer with incorporated developer
(8) Magenta redox dye-releaser layer
(9) Green-sensitive, negative-working, silver halide emulsion layer
(10) Interlayer with incorporated developer
(11) Yellow redox dye-releaser layer
(12) Blue-sensitive, negative-working, silver halide emulsion layer
(13) Gelatin overcoat layer

The timing layer comprised a 1:9 physical mixture by weight of poly(acrylonitrile-co-vinylidene chloride-co-acrylic acid latex) (weight ratio of 14/79/7) and a lactone polymer, partially hydrolyzed and 1-butanol transesterified poly(vinyl acetate-co- maleic anhydride), ratio of acid/butyl ester 15/85.
The "gel nitrate" composition consisted of the following (by weight):
The redox dye-releasers were similar to those described in Research Disclosure, Vol. 182, July 1979, Item 18268, pages 329 through 331. The silver halide emulsion layers were conventional negative-working, 0.25 to 0.65 µ silver chloride emulsions. The incorporated developer was a 3-position blocked 1-phenyl-3-pyrazolidinone. The total gelatin coverage in layers 5 to 13 was 8.1 g/m², hardened with 0.75 percent bis(vinylsulfonyl)methyl ether.
A dye image-receiving element was then prepared by coating the following layers in the order recited on an opaque paper support.

(1) Gelatin (0.81 g/m²) plus formaldehyde equal to 1.25 percent of the total gelatin weight;
(2) Dye image-receiving layer of poly[styrene-co-l-vinylimidazole-co-3-(2-hydroxyethyl)-l-vinylimid- azolium chloride] (weight ratio 50:40:10) (2.4 g/m²); sorbitol (0.54 g/m²) and gelatin (3.0 g/_m ²);
(3) Interlayer of 2-(2-hydroxy-3,5-di-t-amylphenyl)-benzotriazole (0.54 g/m²) and gelatin (0.86 g/_m ²); and
(4) Gelatin (0.65 g/m²) containing zinc sulfate (0.04 g/_m ²).

Samples of the above donor elements were flashed to maximum density, soaked in the activator solution of Example 2 contained in a shallow tray processor for 15 seconds at 28°C, and then laminated between nip rollers to dry samples of the dye image-receiving element. After either 4 or 10 minutes, the donor and receiver were pulled apart. The extent of areas of emulsion and/or timing layer, if any, from the donor which have transferred to the receiver was estimated visually as follows:
The above data indicate that photosensitive elements containing an interlayer of a mixture of a vinylidene chloride copolymer and the neutralizing layer according to the invention exhibit no emulsion areas transferred to the receiver at both a 4 and a 10 minute lamination. This result is better than that obtained with other interlayers or no interlayer, and is also better than the control prior art neutralizing layer.
It should also be noted that the control element coated at less than 81 meq. acid/m² showed poor physical integrity and was not useable for testing.

Example 4 TLB Determination on Cover Sheet

(A) A control cover sheet was prepared by coating the following layers in the order recited on an opaque poly(ethylene terephthalate) film support:

(1) a neutralizing layer of poly(n-butyl acrylate-co-acrylic acid) (30:70 weight ratio) equivalent to 81 meq. acid/m², hardened with 7.5 percent 1,4-butanediol diglycidyl ether;
(2) an interlayer comprising poly(n-butyl acrylate-co-acrylic acid) (30:70 weight ratio) (0.81 g/m²) and poly(acrylonitrile-co-vinylidene chloride-co-acrylic acid) (12:68:20 weight ratio) (0.54 g/m²); and
(3) a timing layer as described in Example 3.

(B) A cover sheet according to the invention was prepared by coating the following layers in the order recited on an opaque poly(ethylene terephthalate) film support:

(1) a neutralizing layer of poly[n-butyl acrylate-co-acrylic acid-co-N-(isobutoxymethyl)acrylamide] (20:70:10 weight ratio) equivalent to 81 meq. acid/m², hardened with 1.5 percent p-toluenesulfonic acid;
(2) an interlayer comprising poly[n-butyl acrylate-co-acrylic acid-co-N-(isobutoxymethyl)acrylamide] (20:70:10 weight ratio) (0.81 g/m²) and poly-(acrylonitrile-co-vinylidene chloride-co-acrylic acid) (12:68:20 weight ratio) (0.54 g/m²); and
(3) a timing layer as described in Example 3.

(C) A cover sheet similar to B was prepared except that layer 1 coverage was equivalent to 48 meq. acid/m^2.
An indicator sheet was prepared consisting of thymolphthalein dye in a gelatin layer coated on a transparent support.
Samples of the indicator sheet were soaked in the activator of Example 1 for 15 seconds at 28°C and then laminated to samples of the above cover sheets by laminating between nip rollers. The change in color of the dye from blue to colorless indicates the TLB (Timing Layer Breakdown) or time required to lower the pH below 12. Samples of the cover sheet were also incubated for various times and conditions as shown in the following Table:
The above data indicate that use of the neutralizing layer according to the invention results in a much more stable TLB than the neutralizing layer in the control element of the prior art. The difference is believed to be due to the fact that unreacted epoxide or other species of the hardening agent in the control element can migrate out of the neutralizing layer to affect the TLB. In using the neutralizing layer of the invention, however, heat or an innocuous acid catalyst is used to internally cross-link the neutralizing layer, so that there is no unreacted species which can wander to the timing layer to affect TLB.

Claims

1. A photographic assemblage comprising:

(a) a support having thereon at least one photosensitive silver halide emulsion layer having associated therewith a dye image-providing material;

(b) a dye image-receiving layer;

(c) a neutralizing layer; and

(d) a timing layer located between said neutralizing layer and said dye image-receiving layer so that processing composition must first permeate said timing layer before contacting said neutralizing layer;
characterized in that said neutralizing layer ^/ comprises a cross-linked polymer derived from:

i) 5 to 30 weight percent of recurring units having the structure:

wherein

R¹ is hydrogen or methyl,

R² is alkylene, arylenealkylene, alkylenebisarylene, arylenebisalkylene or arylene,

R³ is an alkyl group of 1 to 10 carbon atoms, and

n and m are 0 or 1 with the proviso that when m is 0, n is 0, and when m is 1, n is 0 or 1;

ii) at least 30 and up to 90 weight percent of recurring units derived from a substituted or unsubstituted acrylic acid; and

iii) 5 to 30 weight percent of recurring units derived from an alkyl acrylate ester wherein said alkyl group has from 1 to 16 carbon atoms.

2. An assemblage according to claim 1 characterized in that n and m are each 0.

3. An assemblage according to claim 2 characterized in that R¹ is hydrogen and R³ is an isobutyl group.

4. An assemblage according to claim 1 characterized in that said acrylic acid moiety is either acrylic or methacrylic acid.

5. An assemblage according to claim 1 characterized in that said alkyl acrylic ester moiety comprises an alkyl acrylate or methacrylate wherein said alkyl group has from 1 to 6 carbon atoms.

6. An assemblage according to claim 5 characterized in that said alkyl acrylic ester comprises butyl acrylate.

7. An assemblage according to claim 1 characterized in that said polymer comprises poly[N-(isobutoxymethyl)acryl- amide-co-acrylic acid-co-n-butyl acrylate] (10:70:20 weight ratio).

8. An assemblage according to claim 1 characterized in that it also comprises an alkaline processing composition and means containing same for discharge within said assemblage.